Anthraquinonyl carbazoles



Patented Feb. 3, 1931 UNITED STATES PATENT o iCE FRITZ BAUMANN, on r.Evenirnsnn-on-rnn-nnrnn, GERMANY, AssrGnoa To GENERAL ANILINE wonxs, Ind, on NEW YORK, 1v. 2:, A CORPORATION on DELAWARE ANTHRAQUINONYL GAR-BAZOLES No Drawing. Application filed March 8, 1929, Serial No. 345,508, and in Germany 1179101114, 1928.

The present invention relates to vat dyestuffs of the anthraquinoneseries, more par ticularly it relates to compounds of the probable general formula:

wherein at least one as stands for an anthraquinonyl imino residue, being attached to the nucleus by only one linkage in position m and the other ms stand for hydrogen or a mono- 15 valent substituent and wherein all nuclei may be further substituted, for example, by halogen, a hydroxy-', alkyloxyor a substituted amino-group, such as a benzoylamino gr p- J My new compounds are obtainable by re-. acting upon a 2.2 di-a-nthraquinonyl-l.1- carbazole which may be represented by the following formula;

vatedtemperature, say at about 180 (lto about 250 C. for a prolonged time, for instance,

for 3-4 hours. Advantageously the reaction is carried out in a high-boiling organic solvent, such as naphthalene, trichlorobenzene, ethylcarbazole, and in the presence of an acid binding agent,for example, magnesia, sodium 7 acetate, soda or potash, and if desired, in the presence of a suitable catalyst,such as copper or a salt thereof.

In view of the insolubility in organic solvents, the new dyestuffs separate during the reaction and can be easily isolated by filtering, if desired, after previously diluting the mixture with an organic solvent, such as pyridine, toluene, alcohol and the like. .Inor ganic substances, eventually'present, in the dyestuff, can be removed by boiling with diluted nitric acid; organic impurities may be eliminated by boiling with nitrobenz ene, quinolinc and the like.

My newv products generally are red to greyishblack colored powders, sometimes of acrystalline structure. I They are insoluble or scarcely soluble in organicsolvents, and soluble in concentrated sulfuric acid with a blue to reddish brown coloration. Cotton is dyed from the vat red to greyish black r NH: O NH2 7 said compound being obtainable by saponifi-- cation with sulfuric acid of the'corresponding dibenzoyl-compound (compare GermanP'at ent239,5 l9), are heated to boiling while stirring with 14 parts by Weight of 1 p-tolylazimido58-bromo-anthraquinone, 12 parts by weight of water-free potassium acetate, 3

parts by weight of magnesia, and 0.3 parts diluted hydrochloric acid, a dark red crystalline powder is obtained having probably the following formula:

The new dyestu'ff is insoluble in organic solvents, soluble in concentrated sulfuric acid with a blue coloration. On pouring into water the sulfuric acid solution, the dyestufl' is reprecipitated in form or" red flakes. From the Vat cotton is dyed powerful red shades of excellent tastness properties.

Ewamplc 2.-8 parts by weight of 4.4J-diamino-2.2-di-anthraqu nonyl-1.lcarbazole are heated to boiling in 160 parts by weight of nitrobenzene with 9 parts by weight of chloroanthraquinone, l parts by weight of calcined soda, 0.3 parts by weight of copper bronze. W hen the starting material can no longer be detected, the reaction is interrupted and the mixture is sucked at 140-150 C. The dyestutl having the probable formula:

is washed with nitrobenzene, alcohol and water, and is thus obtained in form or a greyish blue colored powder which dissolves in sulfuric acid with an olive green coloration. It is scarcely soluble in organic solvents. From its yellowish-brown vat cotton is dyed corinth shades of excellent fastness properties.

Example 3.-5.6 parts by weight of 5- amino 4c benzoyl-amino 2.2 anthraquinonyl-1.1-carbazole (obtainable by partial saponification at about 50 C. with sulfuric acid of B-benzoyl-amino-d'-benZoyl-amino- 2. 2-dianthraquinonyl-1.1-carbazole) are heated in 120 parts by weight of naphthalene to a temperature of 210 C. with 4 parts by weight of 1-benzoyl-amino-l-chloroanthra- H NH 5 Ell dissolves in sulfuric acid with a reddishbrown coloration. From the vat cotton is blackisl1brown shades.

I claim:

1. As new products vat dyestuffs of th following general formula:

I E 0 NH Z I g I \/V x O z z 2:

wherein at least one x stands for an anthraquinonyl imino residue being attached to the nucleus by only one linkage in the position x, and the other ws stand for substituents of the group consisting of hydrogen and any monovalent substituent and wherein all nuclei may be further substituted, being generally red to greyish colored powders, insoluble in organic solvents, soluble in concentrated sulfuric acid with a blue to reddishbrown coloration and dyeing cotton from the vat red to greyish-black shades of excellent fastness properties.

2. As new products Vat dyestufis of the following general formula:

O 0 ll l ll wherein the ws stand for anthraquinonyl-imino groups, which may be substituted and which are attached to the nuclei by only one linkage in the position :0, being generally red to greyish colored powders, insoluble in organic solvents, soluble in concentrated sulfuric acid with a blue to reddish-brown coloration and dyeing cotton from the at red to greyish-black shades of excellent fastness properties.

3. As a new product the vat dyestuff of the following formula:

0 NHY Y NH O I N N w l I 0' N-N N being a dark red crystalline powder, insoluble in organic solvents, soluble in concentrated sulfuric acid with a blue coloration and dyeing cotton from its vat powerful red shades of excellent fastness properties.

In testimony whereof I have hereunto set my hand.

FRITZ BAUMANN. [L. s.] 

